Modification of cellulose with tetrasulfatoesters of disulfonium salts



United States Patent 7 Claims. 61. 8-120) The present invention relates to new polysulfonium compounds in which the sulfonium groups are intramolecularly neutralized after the manner of betaine compounds. The present invention also relates to a process for improving, particularly for creaseproofing, textile material in which the said polysulfonium compounds are used as finishing agents.

It is known that textile material of fiber-forming substances containing reactive hydrogen atoms, for example of cellulose, regenerated cellulose, wool and mixtures of these materials with each other or with synthetic fibers can be improved by treatment of the material with solutions of sulfur-containing organic compounds which are capable of reacting with the fiber-forming substances with crosslinking, and with alkaline reacting substances. Dihydroxy-diethylsulfone, dihydroxy-diethylsulfoxide and their derivatives have become particularly known as sulfur-containing organic compounds for the said purpose. These substances have the disadvantage, however, that the textile material treated therewith may become yellow. In some cases the toxicity of the substances makes their use difficult.

The disodium salt of tris-(fi-sulfoethyl) sulfonium has recently been recommended as a sulfur-containing organic compound. When using this compound however the high cost of the process is a drawback; this manifests itself in a protracted treatment, usually of more than one stage, which is necessary to carry out the reaction with the textile material, to remove by products and to obviate the yellowing of the treated textile material.

It is an object of the present invention to provide new polysulfoniurn compounds which are distinguished by low toxicity and ready accessibility.

Another object is to impart a creaseproof finish to textile material Without causing it to become yellow.

It is further an object of this invention to carry out the finishing of textile material in a simple and uncomplicated manner.

These and other objects which will be evident from the following description are achieved by the present invention.

We have found that textile material of fiber-forming substances containing reactive hydrogen atoms, preferably of cellulose and regenerated cellulose, can be improved without the said disadvantages by treatment in any sequence with solutions of organic compounds containirlg sulfur and with alkaline reacting substances by using as the sulfur-containing organic compound a substance having the general formula:

in which R denotes an aliphatic, cycloaliphatic, aliphaticcycloaliphatic, aromatic or aliphatic-aromatic radical having one to ten carbon atoms and having a valency of (m+2), R denotes a divalent aliphatic, aromatic or aliphatic-aromatic radical having one to ten carbon atoms, Y denotes a radical having the formula O, S or the radicals indicated by R denote identical or different alkylene groups having two to four carbon atoms, X denotes a radical of sulfuric acid or phosphoric acid attached by an ester bond, n denotes one of the whole numbers from 0 to 25, m denotes one of the whole numbers from 0 to 4 and Q denotes the equivalent of a cation, preferably an alkali metal ion or an unsubstituted or substituted ammonium ion.

Owing to their ready accessibility, those substances having the above Formula I are preferred in which the radicals R and R denote alkylene radicals having one to ten, preferably two to ten, carbon atoms, cyclohexylene radicals or cyclohexylene-alkylene radicals and m is equal to zero.

Sulfur-containing organic compounds having the general Formula II have particular industrial importance:

CHr-CHrO-SOs (II) A denotes a radical having the formula -(CH a radical having the formula (OH O-(CH or a radical having the formula:

CHrOHz-O-SOa III NaO 8-0 Hz-C H2 CHa-CHz-O-SO aNa carom-0403 VII C Ha-C Hr-O SO Na oni-om-o-soa vnr OaS-O The substances having these special formulae but in which the sodium is replaced by potassium or ammonium are also suitable. Sodium salts are however preferred for reasons of economy.

The substances having the above mentioned general formulae may be prepared by conventional chemical reactions. The substances having Formula II may be obtained for example in the following way: A dichloride having the Formula ClA-Cl, in which A has the same meaning as in Formula II, is reacted with twice the molar amount of B-hydroxyethylmercaptan with elimination of hydrogen chloride. This reaction is advantageously carried out in aqueous medium with an addition of an acid-binding agent, such as sodium hydroxide, at a temperature of about 80 C. The substance having the formula:

thus obtained is then reacted with twice the molar amount of B-chloroethanol by dissolving it for example in an excess of B-chloroethanol and boiling the solution until the reaction is completed. A substance having the formula:

HO-CHa- CHa e ClHrCHz-OH sA-s 201 HO-CHz-Cg \CHPCHPOH is thus formed which is converted into a substance having the Formula II by conventional esterification with sulfuric acid, chlorosulfonic acid or o'leum and subsequent neutralization with an alkaline reacting substance, particularly an alkali metal hydroxide or ammonia.

The compounds having the general Formula I or H are used in the form of their solutions, particularly their aqueous solutions. They are applied in the conventional Ways to the fibrous material to be treated, for example by doctoring, spraying, dipping or preferably by padding. It has proved to be advantageous to apply the solutions in such amounts to the material that about 0.05 to 1 mole,

CHn-CHr-O-SOa XII hydroxides, are required in addition to the said solutions 7 for the process according to this invention. These are also preferably used in the form of their aqueous solutions.

The solutions of the alkaline reacting substances and those of the substances having the Formula I or II are applied in any sequence, preferably successively, to the treatment material. Thus the former may be applied first, and then the latter, or vice versa. In general however it is disadvantageous .for the process according to this invention to apply both solutions at the same time because a portion of the substance having the Formula I or 11 may be chemically changed before it comes into contact with the treating material. A modification of the present process which is especially suitable if, as explained further below, conventional resin finishing agents are added, is first to treat the fibrous material with an aqueous solution of a substance having the Formula I or H and then to dip it into an aqueous solution of an alkaline reacting substance. The solution of the alkaline reacting substance may have any temperature between its melting point and its boiling point; it is particularly simple, and therefore preferable, to use the solution of the alkaline reacting substance at room temperature, i.e. at about 15 to 65 C. As a rule it is suflicient to expose the treatment material to the alkaline solution for ten seconds to five minutes; the period of treatment may however be prolonged, for example to fifteen minutes.

When a conventional resin finishing agent is not used, it is preferable first to impregnate the treatment material with the alkaline solution and, after this has reacted for two to twenty minutes, to apply a solution of a substance having Formula I or H to the textile material.

It is particularly advantageous to use, in addition to the substances having the Formula I or II, conventional crosslinking resin finishing agents and if desired acid or potentially acid catalysts for reaction with the fibrous material. Among conventional crosslinking resin finishing agents we include particularly N-methylol compounds of compounds containing urea groups, urethane groups or carboxylic amide groups, for example urea, melamine, ethyleneurea, propylenurea, glyoxal monoureine, glyoxal diureine, adipamide. butanediol diurethane, triazinones, urones, the methylol compound of acetone, ethers of the said methylol compounds with low molecular weight alcohols, fonnals and epoxy componds, such as diglycol diglycidyl ethers and triglycol diglycidyl others. It is advantageous and labour-saving to use the conventional crosslinking resin finishing agents with the substances having the Formula I or II in a single liquor. Concentrations of to 200' g./l. of conventional resin finishing agents have proved to be particularly suitable. When necessary, acid or potentially acid catalysts for the reaction of the conventional resin finishing agents with the textile material may also be added to the liquor. These catalysts are those conventionally used; examples are organic acids of medium strength, such as formic acid or acetic acid, strong inorganic acids, such as sulfuric acid, acid reacting salts of strong acids, such as magnesium chloride, zinc chloride, zinc nitrate or zinc fluoborate, ammonium and amine salts of strong acids, such as ammonium chloride or diethanolammonium chloride.

When conventional resin finishing agents and catalysts therefore are employed, it is recommendable to carry out the process according to this invention as follows:

(1) Padding on an aqueous solution of a substance having the Formula I or II, a conventional resin finishing agent and an acid or potentially acid catalyst,

(2) Drying the treatment material,

(3) Reaction of the conventional resin finishing agent by thermal or dwell tempering, and

(4) Treatment with an alkaline reacting agent to react the compound having the Formula I or II with the fibrous material.

It has also proved to be particularly suitable to add to the aqueous solutions of substances having the Formula I or II, which if desired contain conventional crosslinking resin finishing agents and catalysts therefore, also polymer dispersions or solutions such as are conventionally used in textile resin finishing, for example dispersions of homopolymers and copolymers of acrylic esters, dispersions of polyethylene and solutions of polyacrylamide. Softening agents, such as ethenoxylation products of high molecular weight fatty acids, may also be employed.

The invention is further illustrated by the following examples. The parts and percentages given in the examples are units of weight.

Example 1 A length of cotton imitation poplin having a weight of 132 g./sq. m. is padded at room temperature with an aqueous solution of 80 g./l. of a compound whose constitution corresponds to Formula VII. Squeezed out to 75% liquor take-up and passed through a padding machine containing an aqueous 10% caustic soda solution, again squeezed out to about 100% liquor retention, left for a dwell period of two minutes, rinsed I and washed until neutral. The fabric is dried and conditioned. The technological data which may thereafter be determined may be seen from the table below in column 2, compared with the initial values.

6 Example 2 A length of cloth as used in Example 1 is padded at room temperature with an aqueous solution of g./l. of the chemical substance having Formula VII, 40 g./l. of dimethylolpropyleneurea and 15 g./l. of magnesium chloride (hydrated), squeezed out to a liquor retention of 75 dried at 80 C., conditioned to a residual moisture content of 6 to 8%, heated for five minutes at 150 C. to condense the dimethylolpropyleneurea, then padded with 10% aqueous caustic soda solution, squeezed out to liquor retention left for two minutes, rinsed out at room temperature and washed until neutral. The technological data which can be determined on this cloth are set out in column 3 in the table below.

Example 3 A piece of cloth is finished in the way described in Example 1, using 80 g./l. of a compound according to Formula IV.

The data of the technological testing of the cloth are set out in column 4 of the table below.

Example 4 A piece of fabric is resin finished in the way described in Example 2. 80 g./l. of the chemical compound having the Formula IV is used in addition to the 40 g./l. of dimethylolpropylenurea and 15 g./l. of hydrated magnesium chloride used therein. The data determined in the technological testing of the cloth are given in column 5 in the table below.

Example 5 A piece of cloth as in Example 1 is padded at room temperature with an aqueous solution of 70 g./l. of the chemical substance having the Formula III, 40 g./l. of dimethylolpropylenurea and 15 g./l. of hydrated magnesium chloride, squeezed out to 75% liquor take-up, dried at 80 C., conditioned to a residual moisture content of 7% and heated for five minutes at C. It is then padded again with 10% aqueous caustic soda solution so that a liquor take-up of 100% is achieved. The cloth is left for twenty minutes at room temperature, rinsed and Washed until neutral. The technological data determined on the cloth are set out in column 6 of the table below.

Example 6 The procedure of Example 5 is followed but 80 g./l. of the chemical substance having Formula VI is used instead of 70 g./l. of the chemical substance having Formula III.

The technological data determinable on the finished cloth appear in column 7 of the table below.

Example 7 A cloth as used in Example 1 is padded with aqueous 10% caustic soda solution, a liquor take-up of 70% being achieved. After the cloth has swollen for twenty minutes, it is padded a second time, this time with a solution of 80 g./l. of the chemical substance having Formula IX and to a liquor take-up of 100%. After a reaction period of five minutes at room temperature, the cloth is rinsed thoroughly and neutralized with aqueous acetic acid. The cloth is then squeezed to a liquor retention of 35 to 40% by squeeze rolls and padded a third time, this time also to 100% liquor take-up and with a reaction mixture having the following composition: 80 g./l. of dimethoxydi Example 8 The procedure of Example 7 is followed but 80 g./l. of the substance having the Formula X is used in the second padding operation instead of 80 g./l. of the subforming substances containing reactive hydrogen atoms Which comprises impregnating the textile material in any sequence with:

(a) an aqueous solution of an alkali metal hydroxide stance having the Formula IX. 5 i u 1 f b t h h The technological data are given in column 9 of the an eousl u Ion O a Su 5 ance avmg table belowenera OI'IIIU a.

Example 9 O SO-OHzCH\-r Q9 CH2CHiO-SO Q The procedure of Example 7 is adopted but in the 10 SA-S 2M second padding operation 80 g./ l. of the substance having 6 OHHJHFO SO3G the Formula XII is used instead of 80 g./l. of the subin which A is a member selected from th u Stance having the Formula consistin of radicals havin th f0 1 e gm p The technological data are given in column 10 in the c 6 mm table below. 2) 2)q 2)r In each of the columns 1 to 10, (a) gives the data after d the cloth has been finished, While (b) gives the data after a machine washing at the boil under the following @(Olirhr condition. Liquor ratio: 10:1 with 5 g./l. of soap and 2 g./l. of soda; Washing commenced at C., tempera- 20 p is one of the numbers 1, 2, 3 and 4, q is one of the ture raised Within ten minutes to to C., Washing numbers 2, 3 and 4, r is one of the numbers 2, 3 continued for twenty minutes at this temperature; mateand 4, s is one of the numbers 0, 1 and 2 and M rial then rinsed four times, centrifuged and dried in the is an ion selected from the group consisting of alkali air. metal ions and ammonium ions.

Crease angle dry Crease angle wet Ultimate tensile in )1 according to in )1 according to strength in kg;

DIN 53,890; sum total; sum of warp measurement strip of warp and weft and weft 50 x 200 mm.; according to DIN 53,801

Column 1 untreated cloth:

Column 2 treated according to Example I:

Column 3 treated according to Example 2:

Column 4 treated according to Example 3:

Column 5 treated according to Example 4:

Column 6 treated according to Example 5:

Column 7 treated according to Example 6:

Column 8 treated according to Example 7:

Column 9 treated according to Example 8:

Column 10 treated according t Example 9' We claim:

1. A process for finishing textile material of fiber- 75 2. A process for finishing textile material of fiber-forming substances containing reactive hydrogen atoms which comprises impregnating the textile material in any sequence with:

NEOaS-O-CHrCHg (a) an aqueous solution of an alkali metal hydroxide and (b) an aqueous solution of a substance having the S-CH2S O S-O-OH OH; onz-oni-o-s 03 3. A process for finishing textile material of fiber-forming substances containing reactive hydrogen atoms which comprises impregnating the textile material in any sequence with:

'(a) an aqueous solution of an alkali metal hydroxide and (b) an aqueous solution of a substance having the formula: N303S-CH:CH,$

S-CH1-CH2S o;s-o-orno H, CHa-CHg-O-S 03 4. A process for finishing textile material of fiberforming substances which contain reactive hydrogen atoms which comprises impregnating the textile material in any sequence with:

(a) an aqueous solution of an alkali metal hydroxide and (b) an aqueous solution of a substance having the formula: rams-o-om-orr:

S-CHz-CHr-CHrCHr-S o3so-oH,-orr, CH:CH:O-S0a 5. A process for finishing textile material of fiber-forming substances which contain reactive hydrogen atoms which comprises impregnating the textile material in any sequence with:

(a) an aqueous solution of an alkali metal hydroxide and CHrCHz-O-S ON a (b) an aqueous solution of a substance having the formula:

6. A process for finishing textile material of fiber-forming substances containing reactive hydrogen atoms which comprises impregnating the textile material in any sequence with:

(a) an aqueous solution of an alkali metal hydroxide and (b) an aqueous solution of a substance having the formula:

NQOaSOCHz-CH2 B S( H2)4 2)4S oas-o-onhoin ong-oni-o-soa 7. A process for finishing textile material of fiber-form- 1ng substances containing reactive hydrogen atoms which comprises impregnating the textile material in any sequence with:

(a) an aqueous solution of an alkali metal hydroxide and (b) an aqueous solution of a substance having the ms-m-om-on,

References Cited UNITED STATES PATENTS 3,212,842 10/1965 Burkitt 8120 3,251,642 5/1966 Valentine et a1. 8120 X OTHER REFERENCES Stein et al.: Journal of Organic Chemistry, vol. 11, pp. 664-674 (1946).

Stein et al.: Journal of Organic Chemistry, vol. 11, pp. 692-703 (1946).

NORMAN G. TORCHIN, Primary Examiner, J. CANNON, Assistant Examiner,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,346,325 October 10, 1967 Heinz Bille et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, for that portion of the formula reading column 2, formula IV, for that portion of the formula reading v i e 6 CH CH 0 S0 read CH CH 0 S0 Signed and sealed this 22nd day of April 1969.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A PROCESS FOR FINISHING TEXTILE MATERIAL OF FIBERFORMING SUBSTANCES CONTAINING REACTIVE HYDROGEN ATOMS WHICH COMPRISES IMPREGNATING THE TEXTILE MATERIAL IN ANY SEQUENCE WITH: (A) AN AQUEOUS SOLUTION OF AN ALKALI METAL HYDROXIDE AND (B) AN AQUEOUS SOLUTION OF A SUBSTANCE HAVING THE GENERAL FORMULA: 